Practical 29 Nucleophilic substitution reactions of halogenoalkanes Introduction Li TEST The carbon-halogen bond in halogenoalkanes is polarised: ach student, or par of students, wil eed are Eye protection ca * Rack and 9 test tubes 4 * Labels tpeaieh ote’ The positive charge on the carbon atom makes it attractive 10 negatively Sore nemeeeee ine) charged groups or nucleophiles. Such groups may attack the carbon, Picton tyne ben? displacing the halogen as a halide ion and resuling in a nucleophilic * Stop-ock substitution reaction 1 | Chorobutane” lola a eae SCH + on — Semon i + 2 Bromobutane* + 28romo-2:methypropane rn + Ethanol Nee Ke \ * Siverritrate slo St. SS — Secon + te approximately 0.1 oid”? (solve 7 ty 7 425g 9 250crn of dled water) * Sedum lode Saeeine + Propanone (acetone) SEH scr — Sener + er “with a separate dropping pipette for 7 7 each bole In this practical we will investigate the mechanisms of some nucleophilic substitution reactions by making simple qualitative comparisons of reaction rates, Time requi | double period Procedure Experiment |: Effect of the halogen atom on the rate of hydrolysis In this experiment you will compare the rates of hydrolysis of 1-chlorobutane, ‘'bromobutane, and 1-odobutane (CH3CH,CH,CH,Hal + H,O ——+ CHsCH,CH,CH,OH + H*.4Hal The rate of the reaction can be followed by carrying it out in the presence of silver ions. The halogenoalkanes, being covalently bonded, give no precipitate of silver halide, but as the reaction proceeds and halide ions are produced, a precipitate of silver halide gradually appears: ‘Ag (aq)+Hal~ (aq) —+ AgHal (s) Halogenoalkanes are insoluble in water, so the reaction is carried out in the presence of ethanol, which acts as a mutal solvent for the halogenoalkane and silver ions,A © TARR acier YE PROTECTION able 2 verage bond energies for the carbon— Jogen bends in halogenoalkanes ond ‘Average bond ‘energy/kj mol! “a 339 Br 284 1 218 CARE Eye protection must be worn. Ethanol is highly flammable. Do not have any naked flames near the tubes or the ethanol bottle. Set up three labelled test tubes as described in table 1. Table | “Tubes for experiment Tube | Tube 2 Tube 3 Tem? ethanol em? ethanol lem? ethanol tt 2 drops |-chlorobutane 2 drops bromobutane __2. drops liodobutane Stand the tubes in a beaker of water at about 50°C and put a tube containing Scm? of 0.1moldm~ silver nitrate solution in the same beaker. Leave the tubes for about 10 minutes so that they reach the temperature of the bath, Add Lom? of the silver nitrate solution to each of tubes 1, 2 and 3, working quickly and noting the time. Shake each tube to mix the contents and observe the tubes over the course of the next five minutes or so. 1 Which halogenoalkane undergoes hydrolysis fastest? Which is slowest? 2 Which halogenoalkane has the most polar carbon-halogen bond? 3 1s differing polarity the reason for the different rates of hydrolysis? 4 Suggest a possible explanation for the different rates of hydrolysis using, the bond energies shown in table 2 Theoretical background: the mechanism of nucleophilic substitution Consider the substitution reaction: (R,, Rp, and Ry are allyl groups or hydrogen atoms.) Studies of the kinetics of nucleophilic substitution suggest that these reactions can proceed by wo possible mechanisms. Step-by-step mechanism In tis case, tis proposed that a two step mechanism is involved a A a ® Rs intermediate ‘carbocation & Ry Ry 7 + 70H He Be-G—OH Ry Rs ‘The first step, which is relatively slaw, involves bond cleavage to form the intermediate carbocation, The carbocation is very unstable and reactive, so the second step is fast. The overall rate of the reaction is determined by the slow first step — the rate-determining step. (See Chemistry in Context, Fourth Edition section 25.11 for further discussion of this.)4 Single-step mechanism Here it is proposed that the reaction occurs in a single step. The OH” ion is attracted (0 the central carbon atoms, and as it moves in, it repels the Br atom. At some ‘middle’ stage in the reaction, Br and OH are both partially bonded to the carbon, the OH on its way in and the Br on its way out. This is the transition state of the reaction. It is mot a reaction intermediate which exists independently, but simply the middle stage in a continuous process during which the OH” moves in and the Br” moves out % R, ‘i q on] —= kee oe TSs, Sa a Dou transition state Factors determining which mechanism operates in practice In many nucleophilic substitution reactions, both of the proposed mechan: isms can and do operate, but in most cases one proceeds much faster than the other. The faster mechanism can often be taken as the mechanism for that reaction. In the experiments which follow you will investigate some of the factors which determine the particular mechanism for a given reaction, ‘Two of the most important factors are the structure of the halogenoalkane and the nature of the solvent. A Structure of the balogenoalkane In the first, two-step mechanism, the rate of the reaction is determined by the ease with which the intermediate carbocation forms. If the substituent groups Ry, Ro, and Ry are all alkyl groups rather than H atoms, they will tend to donate electrons, stabilising the carbocation and favouring its formation, R, 8, I +, Rng bee Reg + Ry Ry IF some or all of R,, Ry, and Ry are hydrogen atoms, the formation of the carbocation will be less favoured, so the rate of the overall reaction will be slower. Thus, the two-step mechanism is favoured by the presence of sub- stituent alkyl groups. The reverse applies in the case of the single-step mech anism, which is favoured by the presence of substituent hydrogen atoms. B Nature of the solvent in which the reaction is carried out Polar solvents, particularly water, favour ion formation and therefore the two: step mechanism. Conversely, the single-step mechanism is favoured in non: polar solventsExperiment 2: Effect of the structure of the carbon skeleton on the reaction mechanism and reaction rate ‘The experimental method is similar t0 that in experiment 1, In this case, instead of varying the halogen atom for a given carbon skeleton, we will vary the structure of the alkane skeleton keeping the same halogen, bromine. The bromoalkanes used are ee al Stet I be RBr + H,O —— ROH+H* + Br (using RBr to represent the bromoalkane involved). Jem? ethanol Jom? ethanol \cm? ethanol methylprapane Set up three labelled test tubes as described in table 3, above. In this Add lem? of 0.1moldm™ silver nitrate solution to each tube, working tvemortcnon quickly and noting the time, Shake each tube to mix the contents, Observe MUSTBEWORN the tubes over the course of the next five minutes or So. 5 Which bromoalkane is hydrolysed fastest? Which is slowest? 6 Bearing in mind that the solvent in this experiment is a 1:1 mixture of ethanol and water (the water coming from the silver nitrate solution), which mechanism is likely to be favoured? Explain your answer. 7 Which bromoalkane would be most favoured by the mechanism you have proposed in your answer to question 67 Which would be least favoured? Explain your answer, 8 Explain the observed relative rates of hydrolysis of the three bromoalkanes. Experiment 3: Effect of the solvent on the reaction mechanism and the-reaction rate: the Finkelstein reaction Experiments 1 and 2 have involved hydrolysis reactions in aqueous solution. Its, of course, impossible to carry out hydrolysis in a non-aqueous solvent, but by using a substitution reaction known as Finkelstein's reaction you can investigate the rate of a simple nucleophilic substitution reaction in @ non. aqueous solvent, propanone. The reaction is the substitution of a bromide ion by an iodide ion: RBr+l —> R14 BT The source of I” is sodium iodide. Sodium iodide is soluble in propanone, but sodium bromide is not, As bromide ions are produced in the reaction, they combine with sodium ions to form a precipitate of sodium bromide. RBr(pr) + Na* (pr) +1" (pe) —+ RI(ps) + NaB4(s) I(p8) indicates that the substance is in solution in propanone.] This reaction can therefore be followed by timing the rate of appearance of the sodium bromide precipitate. as© HYEROTECTION —HiGAy MUST BE WORN FLAMMABLE ike ears See Investigation 13 CARE Propanone is highly flammable. Do not have any naked flames near the tubes or the propanone bottle. Dissolve 1g of sodium iodide in 15cm? of propanone. This solution is called Finkelstein’s Reagent Put Scm? of the reagent into each of three labelled test tubes and stand the tubes in a beaker of water at 35°C. Leave the tubes for 10 minutes to reach the temperature of the water bath. ‘Working quickly and noting the time, add 8 drops of 1-bromobutane to the first tube, 8 drops of 2-bromobutane to the second and 8 drops of 2-bromo- 2-methylpropane to the third, Observe the three tubes over the course of the next § minutes or so. 9 Which bromoalkane undergoes nucleophilic substitution by iodide ions fastest? Which is slowest? 10 Bearing in mind that the solvent in this experiment is propanone, which reaction mechanism is likely to be favoured? Explain your answer, 11 Which bromoalkane would be most favoured by the mechanism you have proposed in your answer to question 10? Which would be least favoured? Explain your answer. 12 Explain the observed order of reaction rate of the three bromoalkanes.